Aliphatic Materials and Uses Thereof in Heating and Cooling Applications

ABSTRACT

Aliphatic materials and their use in passive heating and cooling applications are generally disclosed. In some embodiments, dibasic acids and esters (diesters) thereof and their use in passive heating and cooling applications are disclosed. In some embodiments, C18 dibasic acids and esters thereof are disclosed, including their use in passive heating and cooling applications. In some embodiments, various olefins, including alkenes and olefinic acids and esters, are disclosed, including their use in passive heating and cooling applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/099,599, filed Apr. 15, 2016, which claims the benefit ofpriority of U.S. Provisional Application Nos. 62/148,263, filed Apr. 16,2015; and 62/232,235, filed Sep. 24, 2015. Each of the foregoingapplications are hereby incorporated by reference as though set forth intheir entirety herein.

TECHNICAL FIELD

Aliphatic materials and their use in passive heating and coolingapplications are generally disclosed. In some embodiments, dibasic acidsand esters (diesters) thereof and their use in passive heating andcooling applications are disclosed. In some embodiments, C₁₈ dibasicacids and esters thereof are disclosed, including their use in passiveheating and cooling applications. In some embodiments, various olefins,including alkenes, olefinic acids and esters, and diols, are disclosed,including their use in passive heating and cooling applications.

BACKGROUND

Phase-change materials (PCMs) are materials that are capable of storingor releasing energy in a latent manner during a reversible physicalchange of state. For example, such materials can store thermal energyif, in their liquid state, they are exposed to temperatures below theirmelting point, thereby inducing them to solidify and release an amountof energy corresponding to her heat of fusion. They can store thermalenergy when this process is carried out in reverse. Such materials areuseful because they can release and store much more thermal energy thattypical insulating materials of comparable volume.

PCMs are all the more advantageous when the amount of heat exchangedduring these phase changes is large. In the case of a solid/liquidtransition, this is expressed by their heat of fusion or the heat ofcrystallization. The melting temperatures and crystallizationtemperatures of the PCMs furthermore determine the possible applicationsof the material. Typical uses include cooling food products or ofpharmaceutical products that are sensitive to heat, cooling textilematerials, cooling engines, cooling electronic components and circuits,or cooling waste combustion plants. On the industrial scale, PCMs alsoform a means for recovering heat that is released or that is availablecontained in containers or equipment (such as chemical reactors,generators of electrical or mechanical energy) or in process streams orfluids (for example cooling/heating circuits, effluents, etc.),especially during certain exothermic chemical reactions. The heatreleased may then be reused to provide energy to other reactions, whichmakes it possible to reduce the industrial consumption of fossilfuel-derived energy or electrical energy. The use of PCMs in airconditioning cycles (heating/cooling) is also an example of anapplication where it is possible to efficiently store thermal energy tothen release it at the desired time and in the desired amount.

The most common PCM material is water. During its solid/liquidtransition (and therefore implicitly liquid/solid transition), it makesit possible to absorb or release large amounts of heat. It is in thisway that tanks or pools of water at temperatures near 0° C., which isfree (in the form of an ice/liquid water mixture) or is encapsulated,for example in balls made of plastic or other materials, constitute asimple example of a PCM system capable of storing (during the melting ofthe ice) and of releasing (during the crystallization of the liquidwater) large amounts of energy per unit mass of water. But water,although readily available and non-toxic, cannot solve all the possibleproblems due to its restricted usage range (around 0° C.) and problemslinked to the high volume expansion of the ice during its formation.

Other common PCMs include paraffins and fatty acids, such as dodecanoicacid, hydrated salts such as manganese (II) nitrate dihydrate, certaineutectic mixtures, such as mixtures of capric acid and of lauric acid.These compounds generally have quite low melting temperatures, rangingfrom 15 to 48° C. Even so, these PCMs have many drawbacks impeding theirindustrial development. In particular, organic PCMs may be inflammable,have a low thermal conductivity in the solid state, require high heattransfers during the freezing cycle, and have a low volumetric latentheat. Furthermore, paraffins may pose problems of supply, cost andgeneration of CO₂ due to their petroleum origin. Inorganic PCMsgenerate, for their part, significant supercooling phenomena. Moreover,their phase transition temperatures are not constant due, in particular,to their hygroscopicity. Finally, they are capable of resulting in acorrosion of the metals with which they are in contact.

Therefore, there is a continuing need to develop additional PCMs thathave a high heat of fusion, have melting points that occur at practicaltemperatures for various applications, and overcome other of theaforementioned problems.

SUMMARY

In a first aspect, the disclosure provides compounds of formula (I):

wherein: X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted one or more times by substituents selectedindependently from R^(x); R¹ is C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₁₋₁₂oxyalkyl, C₃₋₁₂ cycloalkyl, or C₂₋₁₂ heterocyclyl, each of which isoptionally substituted one or more times by substituents selectedindependently from R^(x), or R¹ is a hydrogen atom; R² is a C₁₋₁₂ alkyl,C₂₋₁₂ alkenyl, C₁₋₁₂ oxyalkyl, C₃₋₁₂ cycloalkyl, or C₂₋₁₂ heterocyclyl,each of which is optionally substituted one or more times bysubstituents selected independently from R^(x), or R² is a hydrogenatom; and R^(x) is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆heteroalkyl, or C₂₋₆ alkenyl.

In a second aspect, the disclosure provides passive heating and coolingcompositions, including one or more compounds of the first aspect.

In a third aspect, the disclosure provides passive heating and coolingcompositions that comprise one or more compounds selected from the groupconsisting of: 9-octadecene, octadecanes, pentadecanes, tridecanes,methyl tridecanoate, and methyl pentadecanoate.

In a fourth aspect, the disclosure provides structures, apparatuses, ormaterials comprising one or more compounds of the first aspect or one ormore compositions of the second or third aspects. In some embodiments,the structures, apparatuses, or materials include the following: polymercomposites (such as a polymer composite comprising metal wires, metalparticles, glass fibers, glass particles, and the like); wax composites(such as a wax composite comprising metal wires, metal particles, glassfibers, glass particles, and the like); insulation materials surroundingparts of a heating apparatus (such as furnaces, ovens, boilers, airducts, pipes, and the like); insulated storage units; food or drinkcontainers; building materials; medical equipment (such as containersfor blood, other biological fluids, and biological tissue, operatingtables, and the like); medical packaging, such as hot-cold therapies;textile fibers; clothing articles, jackets, coats, boots, shoes, hats,gloves, scarves, and the like; waste heat recovery apparatuses; waterheating and cooling apparatuses; heat pump systems; passive storagestructures in bioclimatic buildings; apparatuses for reducing exothermictemperature peaks in chemical reactors or reaction vessels; solar powerplants; space suits; spacecraft; vehicle compartment insulation systems;electronic device insulation systems; battery cell insulation or safetysystems; computer cooling systems; turbine inlet cooling systems;thermal energy storage systems; and telecommunications shelters.

In a fifth aspect, the disclosure provides methods of storing orreleasing thermal energy, the methods comprising: using a compound ofthe first aspect or a composition of the second or third aspects, or astructure, apparatus, or material of the fourth aspect.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

FIG. 1 shows a non-limiting example of a compound made according tocertain embodiments disclosed herein, wherein: X¹ is C₁₁₋₂₄ alkylene orC₁₁₋₂₄ alkenylene, each of which is optionally substituted; R¹ is C₁₋₁₂alkyl, C₂₋₁₂ alkenyl, C₁₋₁₂ oxyalkyl, C₃₋₁₂ cycloalkyl, or C₂₋₁₂heterocyclyl, each of which is optionally substituted, or R¹ is ahydrogen atom; R² is a C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₁₋₁₂ oxyalkyl, C₃₋₁₂cycloalkyl, or C₂₋₁₂ heterocyclyl, each of which is optionallysubstituted, or R² is a hydrogen atom.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “polymer” refers to a substance having a chemicalstructure that includes the multiple repetition of constitutional unitsformed from substances of comparatively low relative molecular massrelative to the molecular mass of the polymer. The term “polymer”includes soluble and/or fusible molecules having chains of repeat units,and also includes insoluble and infusible networks. As used herein, theterm “polymer” can include oligomeric materials, which have only a few(e.g., 5-100) constitutional units

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example, “C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atoms and,for example, includes, but is not limited to, methyl, ethyl, n-propyl,isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl,n-pentyl, neopentyl, and n-hexyl. As a further example, a “C₄₋₁₀ alkene”refers to an alkene molecule having from 4 to 10 carbon atoms, and, forexample, includes, but is not limited to, 1-butene, 2-butene, isobutene,1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene,1-nonene, 4-nonene, and 1-decene.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins includealpha-olefins, wherein the unsaturated carbon-carbon bond is present atone end of the compound. Low-molecular-weight olefins may also includedienes or trienes. Low-molecular-weight olefins may also includeinternal olefins or “low-molecular-weight internal olefins.” In certainembodiments, the low-molecular-weight internal olefin is in the C₄₋₁₄range. Examples of low-molecular-weight olefins in the C₂₋₆ rangeinclude, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, andcyclohexene. Non-limiting examples of low-molecular-weight olefins inthe C₇₋₉ range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene,3-nonene, 1,4,7-octatriene. Other possible low-molecular-weight olefinsinclude styrene and vinyl cyclohexane. In certain embodiments, it ispreferable to use a mixture of olefins, the mixture comprising linearand branched low-molecular-weight olefins in the C₄₋₁₀ range. Olefins inthe C₄₋₁₀ range can also be referred to as “short-chain olefins,” whichcan be either branched or unbranched. In one embodiments, it may bepreferable to use a mixture of linear and branched C₄ olefins (i.e.,combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “acid,” “acids,” “carboxylic acid,” or “carboxylicacids” refer to compounds having the general formula: R—COOH, wherein Rdenotes any organic moiety (such as alkyl, aryl, or silyl groups),including those bearing heteroatom-containing substituent groups. Incertain embodiments, R denotes alkyl, alkenyl, aryl, or alcohol groups.In certain embodiments, the term “acids” or “carboxylic acids” may referto a group of compounds with the general formula described above,wherein the compounds have different carbon lengths.

As used herein, “alcohol” or “alcohols” refer to compounds having thegeneral formula: R—OH, wherein R denotes any organic moiety (such asalkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “alcohol” or “alcohols” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. As used herein, the term “alkanol” refers toalcohols where R is an alkyl group.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₁₋₆ alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group. Also, in someinstances, one or more of the carbon atoms in the alkyl or alkylenegroup can be replaced by a heteroatom (e.g., selected from nitrogen,oxygen, or sulfur, including N-oxides, sulfur oxides, and sulfurdioxides, where feasible), and is referred to as a “heteroalkyl” or“heteroalkylene” group, respectively. Non-limiting examples include“oxyalkyl” or “oxyalkylene” groups, which are groups of the followingformulas: -[-(alkylene)-O-]_(x)-alkyl, or-[-(alkylene)-O-]_(x)-alkylene-, respectively, where x is 1 or more,such as 1, 2, 3, 4, 5, 6, 7, or 8.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number ofcarbon atoms in an alkenyl group is represented by the phrase “C_(x-y)alkenyl,” which refers to an alkenyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkenyl”represents an alkenyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethenyl, 2-propenyl,2-butenyl, and 3-butenyl. In some instances, the “alkenyl” group can bedivalent, in which case the group can alternatively be referred to as an“alkenylene” group.

As used herein, “cycloalkyl” refers to an aliphatic saturated orunsaturated hydrocarbon ring system having 1 to 20 carbon atoms, whichmay be optionally substituted, as herein further described, withmultiple degrees of substitution being allowed. In some embodiments, theterm refers only to saturated hydrocarbon ring systems, substituted asindicated above. Examples of “cycloalkyl,” as used herein, include, butare not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclohexenyl, cycloheptyl, cyclooctyl, adamantyl, and the like. Thenumber of carbon atoms in a cycloalkyl group is represented by thephrase “C_(x-y) cycloalkyl,” which refers to a cycloalkyl group, asherein defined, containing from x to y, inclusive, carbon atoms. Thus,“C₃₋₁₀ cycloalkyl” represents a cycloalkyl having from 3 to 10 carbonatoms and, for example, includes, but is not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl,cyclooctyl, and adamantyl. In some instances, the “cycloalkyl” group canbe divalent, in which case the group can alternatively be referred to asa “cycloalkylene” group. Cycloalkyl and cycloalkylene groups can also bereferred to herein as “carbocyclic rings.” Also, in some instances, oneor more of the carbon atoms in the cycloalkyl or cycloalkylene group canbe replaced by a heteroatom (e.g., selected independently from nitrogen,oxygen, silicon, or sulfur, including N-oxides, sulfur oxides, andsulfur dioxides, where feasible), and is referred to as a “heterocyclyl”or “heterocyclylene” group, respectively. The term “heterocyclic ring”can also be used interchangeable with either of these terms. In someembodiments, the cycloalkyl and heterocyclyl groups are fully saturated.In some other embodiments, the cycloalkyl and heterocyclyl groups cancontain one or more carbon-carbon double bonds.

As used herein, the term “branched,” for example, in reference to analkyl or alkenyl group, refers to the presence of one or more carbonatoms having three or four connections to other carbon atoms. Bycontrast, the term “unbranched” refers to groups not having any carbonatoms with three or four connections to other carbon atoms. For example,groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl arebranched, and groups such as n-propyl and n-butyl are unbranched. Insome instances, it may be desirable to refer to a position for thebranching, such as in the alcoholic portion of an ester. In suchinstances, the carbon atom immediately adjacent to the oxygen atom onthe alcoholic side of the ester is the 1-position, the next in the2-position, and so on. Thus, the alkyl group of sec-butyl alcohol orisopropyl alcohol is said to be branched at the 1-position, and thealkyl group of isobutyl alcohol is said to be branched at the 2-positionand not branched at the 1-position, and so forth. The same principlesapply to alkenyl groups, as the double bond does not count as 2connections. Thus, groups like 9-octedenenyl are said to be unbranched,while a group like 1-methyl-9-octadenenyl is said to be branched, i.e.,at the 1-position.

As used herein, “halogen” or “halo” refers to a fluorine, chlorine,bromine, and/or iodine atom. In some embodiments, the terms refer tofluorine or chlorine.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week, or a compound which maintains its integrity long enoughto be useful for therapeutic or prophylactic administration to apatient. As used herein, the phrases “substituted with one or more . . .” or “substituted one or more times . . . ” refer to a number ofsubstituents that equals from one to the maximum number of substituentspossible based on the number of available bonding sites, provided thatthe above conditions of stability and chemical feasibility are met.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Compounds for Passive Heating and Cooling

In certain aspects, the disclosure provides compounds that are dibasicacids or esters thereof (e.g., diesters formed from various aliphaticalcohols). In some embodiments, the dibasic acid is a C₁₄₋₂₄ aliphaticdibasic acid, such as a C₁₈ aliphatic dibasic acid (e.g., 1,18octadecanedioic acid). In some embodiments, the phase-change compoundsare aliphatic diesters of any of the aforementioned dibasic acids, suchas dimethyl esters.

In a some embodiments, the disclosure provides compounds of formula (I):

wherein: X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted one or more times by substituents selectedindependently from R^(x); R¹ is C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₁₋₁₂oxyalkyl, C₃₋₁₂ cycloalkyl, or C₂₋₁₂ heterocyclyl, each of which isoptionally substituted one or more times by substituents selectedindependently from R^(x), or R¹ is a hydrogen atom; R² is a C₁₋₁₂ alkyl,C₂₋₁₂ alkenyl, C₁₋₁₂ oxyalkyl, C₃₋₁₂ cycloalkyl, or C₂₋₁₂ heterocyclyl,each of which is optionally substituted one or more times bysubstituents selected independently from R^(x), or R² is a hydrogenatom; and R^(x) is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆heteroalkyl, or C₂₋₆ alkenyl.

In some embodiments of any of the aforementioned embodiments, X¹ isC₁₁₋₂₄ alkylene, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some further suchembodiments, X¹ is C₁₁₋₂₄ alkylene, which is optionally substituted oneor more times by substituents selected independently from the groupconsisting of —OH and C₁₋₆ oxyalkyl. In some further such embodiments,X¹ is C₁₂₋₂₀ alkylene, which is optionally substituted one or more timesby substituents selected independently from the group consisting of —OHand C₁₋₆ oxyalkyl. In some further such embodiments, X¹ is —(CH₂)₁₂—,—(CH₂)₁₄—, —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₂₀—, or —(CH₂)₂₂—. In somefurther embodiments, X¹ is —(CH₂)₁₆—.

In some embodiments of any of the aforementioned embodiments, X¹ isC₁₁₋₂₄ alkenylene, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some further suchembodiments, X¹ is C₁₁₋₂₄ alkenylene, which is optionally substitutedone or more times by substituents selected independently from the groupconsisting of —OH and C₁₋₆ oxyalkyl. In some further such embodiments,X¹ is C₁₂₋₂₀ alkenylene, which is optionally substituted one or moretimes by substituents selected independently from the group consistingof —OH and C₁₋₆ oxyalkyl. In some further such embodiments, X¹ is—(CH₂)₇—CH═CH—(CH₂)₇—. In the aforementioned embodiments, thecarbon-carbon double bond(s) can have a Z or E configuration, or somecombination thereof. In some embodiments, however, the alkenylene grouphas one carbon-carbon double bond and has a Z configuration, such as—(CH₂)₇—CH═CH—(CH₂)₇— having a Z configuration. In some otherembodiments, the alkenylene group has one carbon-carbon double bond andhas an E configuration, such as —(CH₂)₇—CH═CH—(CH₂)₇— having a Econfiguration.

In some embodiments of any of the aforementioned embodiments, R¹ is ahydrogen atom.

In some embodiments of any of the aforementioned embodiments, R¹ isC₁₋₁₂ alkyl, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some further suchembodiments, R¹ is an unbranched C₁₋₁₂ alkyl, which is optionallysubstituted one or more times by substituents selected independentlyfrom the group consisting of —OH and C₁₋₆ oxyalkyl. In some further suchembodiments, R¹ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,or octyl. In some such embodiments, R¹ is methyl. In some suchembodiments, R¹ is ethyl. In some such embodiments, R¹ propyl. In someother embodiments, R¹ is —CH₂—OH, —CH₂—CH₂—OH, —CH(—CH₃)—CH₂—OH, or—CH₂—CH(—OH)—CH₃. In some other embodiments, R¹ is a branched C₁₋₁₂alkyl, which is optionally substituted one or more times by substituentsselected independently from the group consisting of —OH and C₁₋₆oxyalkyl. In some further such embodiments, R¹ is a branched C₁₋₁₂ alkylthat comprises branching at the α-position (i.e., at the carbon atomimmediately adjacent to the alcoholic oxygen of the ester group), suchas where R¹ is isopropyl, sec-butyl, or tert-butyl. In some embodiments,R¹ is a branched C₁₋₁₂ alkyl that comprises branching at the β-position(i.e., at the second carbon atom from the alcoholic oxygen of the estergroup), such as where R¹ is isobutyl or 2-ethylhexyl. In someembodiments, R¹ is 2-ethylhexyl. In some embodiments, R¹ is a branchedC₁₋₁₂ alkyl that comprises branching at the ψ-position (i.e., at thepenultimate carbon atom from the alcoholic oxygen of the ester group),such as where R¹ is isobutyl, isoamyl, neopentyl, or3,5,5-trimethylhexyl. In some embodiments, R¹ is isoamyl(3-methylbutyl). In some embodiments, R¹ is 3,5,5-trimethylhexyl.

In some embodiments of any of the aforementioned embodiments, R¹ isC₁₋₁₂ oxyalkyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of —OH andC₁₋₆ oxyalkyl. In some embodiments, R¹ is selected from the groupconsisting of: —CH₂—CH₂—O—R³, —CH₂—CH(O—R⁴)—CH₃, —CH₂—CH₂—CH₂—O—R⁵,—CH₂—CH₂—CH₂—CH₂—O—R⁶, —CH₂—CH₂(—O—CH₂—CH₂)_(w)—OH,—CH₂—CH₂(—O—CH₂—CH₂)_(x)—O—R⁷; —CH₂—CH(—CH₃)(—O—CH₂—CH(—CH₃))_(y)—OH,and —CH₂—CH(—CH₃)(—O—CH₂—CH(—CH₃))_(z)—O—R⁸; wherein R³, R⁴, R⁵, R⁶, R⁷,and R⁸ are independently methyl or ethyl; and w, x, y, and z areindependently an integer from 1 to 10. In some embodiments, w, x, y, andz are independently 1, 2, or 3. In some embodiments, w, x, y, and z areindependently 4, 5, or 6. In some such embodiments, R¹ is—CH₂—CH₂—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂—O—CH₂—CH₂—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₁₋₁₀—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₂—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₃—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₄—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₅—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₆—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₇—O—CH₃. In some such embodiments, R¹ is—CH₂—CH₂(—O—CH₂—CH₂)₈—O—CH₃.

In some embodiments of any of the aforementioned embodiments, R¹ isC₃₋₁₂ cycloalkyl, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some suchembodiments, R¹ is cyclopentyl. In some such embodiments, R¹ iscyclohexyl.

In some embodiments of any of the aforementioned embodiments, R² is ahydrogen atom.

In some embodiments of any of the aforementioned embodiments, R² isC₁₋₁₂ alkyl, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some further suchembodiments, R² is an unbranched C₁₋₁₂ alkyl, which is optionallysubstituted one or more times by substituents selected independentlyfrom the group consisting of —OH and C₁₋₆ oxyalkyl. In some further suchembodiments, R² is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,or octyl. In some such embodiments, R² is methyl. In some suchembodiments, R² is ethyl. In some such embodiments, R² propyl. In someother embodiments, R² is —CH₂—OH, —CH₂—CH₂—OH, —CH(—CH₃)—CH₂—OH, or—CH₂—CH(—OH)—CH₃. In some other embodiments, R² is a branched C₁₋₁₂alkyl, which is optionally substituted one or more times by substituentsselected independently from the group consisting of —OH and C₁₋₆oxyalkyl. In some further such embodiments, R² is a branched C₁₋₁₂ alkylthat comprises branching at the α-position (i.e., at the carbon atomimmediately adjacent to the alcoholic oxygen of the ester group), suchas where R² is isopropyl, sec-butyl, or tert-butyl. In some embodiments,R² is a branched C₁₋₁₂ alkyl that comprises branching at the β-position(i.e., at the second carbon atom from the alcoholic oxygen of the estergroup), such as where R² is isobutyl or 2-ethylhexyl. In someembodiments, R² is 2-ethylhexyl. In some embodiments, R² is a branchedC₁₋₁₂ alkyl that comprises branching at the ψ-position (i.e., at thepenultimate carbon atom from the alcoholic oxygen of the ester group),such as where R² is isobutyl, isoamyl, neopentyl, or3,5,5-trimethylhexyl. In some embodiments, R² is isoamyl(3-methylbutyl). In some embodiments, R² is 3,5,5-trimethylhexyl.

In some embodiments of any of the aforementioned embodiments, R² isC₁₋₁₂ oxyalkyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of —OH andC₁₋₆ oxyalkyl. In some embodiments, R² is selected from the groupconsisting of: —CH₂—CH₂—O—R¹³, —CH₂—CH(O—R¹⁴)—CH₃, —CH₂—CH₂—CH₂—O—R¹⁵,—CH₂—CH₂—CH₂—CH₂—O—R¹⁶, —CH₂—CH₂(—O—CH₂—CH₂)_(w′)—OH,—CH₂—CH₂(—O—CH₂—CH₂)_(x′)—O—R¹⁷, —CH₂—CH(—CH₃)(—O—CH₂—CH(—CH₃))_(y′)—OH,and —CH₂—CH(—CH₃)(—O—CH₂—CH(—CH₃))_(z′)—O—R¹⁸, wherein R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, and R¹⁸ are independently methyl or ethyl; and w′, x′, y′, andz′ are independently an integer from 1 to 10. In some embodiments, w′,x′, y′, and z′ are independently 1, 2, or 3. In some embodiments, w′,x′, y′, and z′ are independently 4, 5, or 6. In some such embodiments,R² is —CH₂—CH₂—O—CH₃. In some such embodiments, R² is—CH₂—CH₂—O—CH₂—CH₂—O—CH₃. In some such embodiments, In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₁₋₁₀—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₂—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₃—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₄—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₅—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₆—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₇—O—CH₃. In some suchembodiments, R² is —CH₂—CH₂(—O—CH₂—CH₂)₈—O—CH₃.

In some embodiments of any of the aforementioned embodiments, R² isC₃₋₁₂ cycloalkyl, which is optionally substituted one or more times bysubstituents selected independently from R^(x). In some suchembodiments, R² is cyclopentyl. In some such embodiments, R² iscyclohexyl.

In some embodiments of any of the aforementioned embodiments, R¹ and R²are the same. In some other embodiments of any of the aforementionedembodiments, R¹ and R² are not the same.

In addition to the compounds of formula (I), other compounds may also besuitable for use in passive heating and cooling applications. In someembodiments, such compounds include various hydrocarbons, such asolefins and paraffins. In some other embodiments, such compounds includelong-chain diols such as compounds of formula (II):

OH—X²—OH  (II)

wherein X² is C₁₁₋₂₄ alkylene. In some embodiments, X² is —(CH₂)₁₂—,—(CH₂)₁₄—, —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₂₀—, or —(CH₂)₂₂—. In someembodiments, X² is —(CH₂)₁₈—.

The compounds disclosed above are not limited to any particular use orapplication. In some embodiments, they can be suitable for use asplasticizers, e.g., for polymer resins. They can be suitable for otheruses as well.

Compositions for Passive Heating and Cooling

In further aspects, the disclosure provides passive heating and coolingcompositions, which include one or more compounds of any of theaforementioned embodiments (i.e., phase-change compounds).

In some further aspects, the disclosure also provides passive heatingand cooling compositions that comprise one or more phase-changecompounds selected from the group consisting of: 9-octadecene,octadecanes, pentadecanes, tridecanes, methyl tridecanoate, and methylpentadecanoate. In some embodiments, the phase-change compound in thecomposition is 9-octadecene. In some embodiments, the phase-changecompound in the composition is methyl tridecanoate. In some embodiments,the phase-change compound in the composition is methyl penadecanoate. Insome embodiments, the phase-change compounds in the composition areoctadecanes, such as n-octadecane. In some embodiments, the phase-changecompounds in the composition are pentadecanes, such as n-pentadecane. Insome embodiments, the phase-change compounds in the composition aretridecanes, such as n-tridecane.

These compositions can include one or more of the compounds disclosedherein in any suitable amount. In some embodiments, the compositionincludes the phase-change compounds, wherein the phase change compoundsmake up at least 50% by weight, or at least 60% by weight, or at least70% by weight, or at least 80% by weight of the composition, based onthe total weight of the composition. In some embodiments, thecomposition is made up almost entirely of the phase-change compounds.For example, in some embodiments, the phase change compounds make up atleast 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of the composition, based on the totalweight of the composition. In some embodiments, the composition consistsessentially of the phase-change compounds. In some embodiments, thecomposition consists of the phase-change compounds. In any of theaforementioned embodiments, the composition can include one phase-changecompound, or, in some other embodiments, can include two or morephase-change compounds.

The compositions can be packaged in any suitable form. For example, insome embodiments, the composition is dispersed or mixed into anothermedium, such as a polymer, a ceramic material, concrete, etc. In someembodiments, the composition is physically applied or coated onto thesurface of a material, such as on the surface of a fiber. For example,in some embodiments, the composition is applied to the surface of afiber, and is then held substantially in place by the weaving ofmultiple fibers together, e.g., such that the composition is physicallyheld between multiple fibers. In some other embodiments, however, thecomposition is encapsulated or contained in another material, such as ina polymeric or waxy encapsulant. In some embodiments, such encapsulantsare mixed or dispersed into another medium, such as a polymer, ceramic,concrete, etc. In some other embodiments, however, the composition iscontained within a physical structure, such as a physical compartmentthat is disposed adjacent to (e.g., partially surrounding) anotherstructure, such as a heating device, a cooling device, an electronic ormicroelectronic structure, a battery cell, an insulated cavity, etc.

Items Incorporating Passive Heating and Cooling Compounds orCompositions

In further aspects, the disclosure provides various items (e.g.,structures, apparatuses, materials, etc.) that include one or morephase-change compounds of any of the aforementioned embodiments or oneor more compositions of any of the aforementioned embodiments thatinclude phase-change compounds. In some embodiments, the structures,apparatuses, or materials include the following: polymer composites(such as a polymer composite comprising metal wires, metal particles,glass fibers, glass particles, and the like); wax composites (such as awax composite comprising metal wires, metal particles, glass fibers,glass particles, and the like); insulation materials surrounding partsof a heating apparatus (such as furnaces, ovens, boilers, air ducts,pipes, and the like); insulated storage units; food or drink containers;building materials; medical equipment (such as containers for blood,other biological fluids, and biological tissue, operating tables, andthe like); medical packaging, such as hot-cold therapies; textilefibers; clothing articles, jackets, coats, boots, shoes, hats, gloves,scarves, and the like; waste heat recovery apparatuses; water heatingand cooling apparatuses; heat pump systems; passive storage structuresin bioclimatic buildings; apparatuses for reducing exothermictemperature peaks in chemical reactors or reaction vessels; solar powerplants; space suits; spacecraft; vehicle compartment insulation systems;electronic device insulation systems; battery cell insulation or safetysystems; computer cooling systems; turbine inlet cooling systems;thermal energy storage systems; and telecommunications shelters.

Use of Passive Heating and Cooling Compounds, Compositions, orStructures

In a further aspects, the disclosure provides methods of storing orreleasing thermal energy, the methods comprising: using one or morephase-change compounds of any of the aforementioned embodiments or oneor more phase-change compositions of any of the aforementionedembodiments, or one or more of the phase-change structures of any of theaforementioned embodiments.

In some embodiments, the methods are methods for storing thermal energy.In some such embodiments, the using includes: providing one or morephase-change compounds of any of the aforementioned embodiments (e.g.,as part of a composition of any of the aforementioned embodiments),wherein at least a portion of the phase-change compounds in thecomposition are in a solid state; and exposing the composition to athermal environment having a temperature above the melting point of atleast one of the phase-change compounds in the composition (i.e., wheresaid at least one compound was at least partly in a solid state).

In some embodiments, the methods are methods for releasing thermalenergy. In some such embodiments, the using includes: providing one ormore phase-change compounds of any of the aforementioned embodiments(e.g., as part of a composition of any of the aforementionedembodiments), wherein at least a portion of the phase-change compoundsin the composition are in a liquid state; and exposing the compositionto a thermal environment having a temperature below the melting point ofat least one of the phase-change compounds in the composition (i.e.,where said at least one compound was at least partly in a liquid state).

The using can include any suitable manner of using the aforementionedphase-change compounds, compositions, or structures. Such usingincludes, but is not limited to, incorporating the one or morephase-change compounds (e.g., as part of a phase-change composition or aphase-change structure) into one of more of the following: a polymercomposite (such as a polymer composite comprising metal wires, metalparticles, glass fibers, or glass particles); a wax composite (such as awax composite comprising metal wires, metal particles, glass fibers, orglass particles); insulation material surrounding parts of an heatingapparatus (such as furnaces, ovens, boilers, air ducts, pipes, and thelike); insulated storage units; food or drink containers; buildingmaterials; medical equipment (such as containers for blood, otherbiological fluids, and biological tissue, and operating tables); medicalpackaging, such as hot-cold therapies); textile fibers; clothingarticles, jackets, coats, boots, shoes, hats, gloves, scarves, and thelike; waste heat recovery apparatuses; water heating and coolingapparatuses; heat pump systems; passive storage structures inbioclimatic buildings; apparatuses for reducing exothermic temperaturepeaks in chemical reactors or reaction vessels; solar power plants;space suits; spacecraft; vehicle compartment insulation systems;electronic device insulation systems; battery cell insulation and/orsafety systems; computer cooling systems; turbine inlet cooling systems;thermal energy storage systems; and telecommunications shelters.

Methods of Making Diesters

The diacids and diesters disclosed above can be made by conventionalmeans. For example, in some embodiments, the diesters are made byreacting a dibasic acid with an alcohol or a mixture of alcohols toprovide the dibasic ester by condensation. In some instances, diesterscan also be made by transesterification, where a dibasic ester, such asa dimethyl dibasic ester is reacted with a longer-chain alcohol ormixture of longer-chain alcohols to provide the dibasic ester.

Derivation from Renewable Sources

The compounds employed in any of the aspects or embodiments disclosedherein can, in certain embodiments, be derived from renewable sources,such as from various natural oils or their derivatives. Any suitablemethods can be used to make these compounds from such renewable sources.Suitable methods include, but are not limited to, fermentation,conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt%) or greater (e.g., 99wt% or greater) triglycerides of fatty acids. Major fatty acids in thepolyol esters of soybean oil include but are not limited to saturatedfatty acids such as palm itic acid (hexadecanoic acid) and stearic acid(octadecanoic acid), and unsaturated fatty acids such as oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin (or short-chainolefin) is in the C₂₋₆ range. As a non-limiting example, in oneembodiment, the low-molecular-weight olefin may comprise at least oneof: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. In someembodiments, the short-chain olefin is 1-butene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, the unsaturatedesters may be derived from a natural oil feedstock, in addition to othervaluable compositions. Moreover, in some embodiments, a number ofvaluable compositions can be targeted through the self-metathesisreaction of a natural oil feedstock, or the cross-metathesis reaction ofthe natural oil feedstock with a low-molecular-weight olefin ormid-weight olefin, in the presence of a metathesis catalyst. Suchvaluable compositions can include fuel compositions, detergents,surfactants, and other specialty chemicals. Additionally,transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, multiple metathesis reactions can also beemployed. In some embodiments, the multiple metathesis reactions occursequentially in the same reactor. For example, a glyceride containinglinoleic acid can be metathesized with a terminal lower alkene (e.g.,ethylene, propylene, 1-butene, and the like) to form 1,4-decadiene,which can be metathesized a second time with a terminal lower alkene toform 1,4-pentadiene. In other embodiments, however, the multiplemetathesis reactions are not sequential, such that at least one otherstep (e.g., transesterification, hydrogenation, etc.) can be performedbetween the first metathesis step and the following metathesis step.These multiple metathesis procedures can be used to obtain products thatmay not be readily obtainable from a single metathesis reaction usingavailable starting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

For example, multiple metathesis can be employed to make the dibasicacid compounds used to make the diesters disclosed herein. In someembodiments, alkyl (e.g., methyl) esters of 9-decenoic acid,9-undecenoic acid, 9-dodecenoic acid, or any combination thereof, can bereacted in a self-metathesis reaction or a cross-metathesis to generatevarious unsaturated dibasic alkyl esters, such as dimethyl9-octadecendioate. Such compounds can then be converted to dibasic acidsby hydrolysis or via saponification followed by acidification. If asaturated dibasic acid is desired, the compound can be hydrogenated,either before conversion to the acid or after. Dibasic acids of otherchain lengths can be made by analogous means.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described below with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The rector design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than —40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

EXAMPLES Example 1 Bis(4-methylbutyl) Octadecanedioate

1,18-Octadecanedioic acid (ODDA) was added to a 100-mL three-neckedround-bottom flask. A Dean-Stark condenser was attached, followed by theaddition of toluene to the ODDA and to the trap. 4-Methylbutyl (isoamyl)alcohol was added to the ODDA mixture. The flask was immediately purgedwith nitrogen gas and p-toluenesulfonic acid was added. The reactionmixture was heated and the reaction proceeded for several hours. Heatwas then removed and the reaction mixture was allowed to cool, at whichpoint aqueous NaHCO₃ was added to achieve a neutral pH. After vigorousstirring, the organic layer was separated and dried over Na₂SO₄. Thedried product was then subjected to a vacuum treatment to remove anyresidual solvent.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The bis(3-methylbutyl)octadecanedioate was determined to have a melting temperature (T_(m)) of38.5° C. and an enthalpy of fusion of 148 J/g, indicating itssuitability as a phase-change material for applications where there is adesire to maintain a temperature near human body temperature.

Example 2 Bis(3,5,5-trimethylhexyl) Octadecanedioate

Bis(3,5,5-trimethylhexyl) octadecanedioate was made from octadecanedioicacid (ODDA) and 3,5,5-trimethylhexyl alcohol by means analogous to thoseused for Example 1.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The bis(3,5,5-trimethylhexyl)octadecanedioate was determined to have a melting temperature (T_(m)) of20.5° C. and an enthalpy of fusion of 119 J/g, indicating itssuitability as a phase-change material for applications where there is adesire to maintain a temperature near room temperature.

Example 3 Bis(3,5,5-trimethylhexyl) Octadecanedioate

Bis(triethylene glycol monomethyl ether) octadecanedioate was made fromoctadecanedioic acid (ODDA) and triethylene glycol monomethyl ether bymeans analogous to those used for Example 1.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The bis(triethylene glycolmonomethyl ether) octadecanedioate was determined to have a meltingtemperature (T_(m)) of 15.4° C. and an enthalpy of fusion of 148 J/g,indicating its suitability as a phase-change material for applicationswhere there is a desire to maintain a temperature somewhat below roomtemperature, such as for wine storage.

Example 4 Dimethyl Octadecanedioate

Dimethyl 1,18-octadecanedioate was obtained from Elevance RenewableSciences, Inc. (Woodridge, Ill., USA) in substantially pure form.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The dimethyl1,18-octadecanedioate was determined to have a melting temperature(T_(m)) of 57.1° C. and an enthalpy of fusion of 209 J/g, indicating itssuitability as a phase-change material for applications where there is adesire to maintain a temperature somewhat above room temperature, suchas for a food serving line.

Example 5 Octadecanedioic Acid

1,18-Octadecanedioic acid (ODDA) was obtained from Elevance RenewableSciences, Inc. (Woodridge, Ill., USA) in substantially pure form.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The 1,18-octadecanedioic acidwas determined to have a melting temperature (T_(m)) of 130.2° C. and anenthalpy of fusion of 219 J/g, indicating its suitability as aphase-change material for applications where there is a desire tomaintain an elevated temperature.

Example 6 Octadecane diol

1,18-Octadecane diol was obtained by hydrogenating the ODDA fromElevance Renewable Sciences, Inc. (Woodridge, Ill., USA).

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The 1,18-octadecane diol wasdetermined to have a melting temperatures (T_(m)) of 92.2° C. and 97.5°C., and an enthalpy of fusion of 103 J/g and 85 J/g, respectively,indicating its suitability as a phase-change material for applicationswhere there is a desire to maintain a temperature near the boilingtemperature of water.

Example 7 Dimethyl cis/trans-1,18-Octadec-9-enedioate

Dimethyl cis/trans-1,18-octadec-9-enedioate was obtained from ElevanceRenewable Sciences, Inc. (Woodridge, Ill., USA) in substantially pureform.

The melting point and enthalpy of fusion were determined usingdifferential scanning calorimetry (DSC). The dimethylcis/trans-1,18-octadec-9-enedioate was determined to have a meltingtemperature (T_(m)) of 26.8° C. and an enthalpy of fusion of 259 J/g,indicating its suitability as a phase-change material for applicationswhere there is a desire to maintain a temperature near room temperature.

1. A method of storing or releasing thermal energy, the methodcomprising: using a compound of formula (I):

wherein: X¹ is —(CH₂)₁₆— or —(CH₂)₁₈—; R¹ is C₁₋₁₂ alkyl, which isoptionally substituted one or more times by —OH; and R² is C₁₋₁₂ alkyl,which is optionally substituted one or more times by —OH. 2-5.(canceled)
 6. The method of claim 1, wherein X¹ is —(CH₂)₁₆—. 7.(canceled)
 8. (canceled)
 9. The method of claim 1, wherein R¹ is anunbranched C₁₋₁₂ alkyl, which is optionally substituted one or moretimes by —OH.
 10. The method of claim 9, wherein R¹ is methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl.
 11. The method of claim9, wherein R¹ is —CH₂—OH, —CH₂—CH₂—OH, —CH(—CH₃)—CH₂—OH, or—CH₂—CH(—OH)—CH₃.
 12. The method of claim 1, wherein R¹ is a branchedC₁₋₁₂ alkyl, which is optionally substituted one or more times by —OH.13. The method of claim 12, wherein R¹ is a branched C₁₋₁₂ alkyl thatcomprises branching at the α-position.
 14. The method of claim 13,wherein R¹ is isopropyl, sec-butyl, or tert-butyl.
 15. The method ofclaim 12, wherein R¹ is a branched C₁₋₁₂ alkyl that comprises branchingat the β-position.
 16. The method of claim 15, wherein R¹ is isobutyl or2-ethylhexyl.
 17. The method of claim 12, wherein R¹ is a branched C₁₋₁₂alkyl that comprises branching at the ψ-position.
 18. The method ofclaim 17, wherein R¹ is isobutyl, isoamyl, neopentyl, or3,5,5-trimethylhexyl. 19-24. (canceled)
 25. The method of claim 9,wherein R² is an unbranched C₁₋₁₂ alkyl, which is optionally substitutedone or more times by —OH.
 26. The method of claim 25, wherein R² ismethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl.
 27. Themethod of claim 25, wherein R² is —CH₂—OH, —CH₂—CH₂—OH,—CH(—CH₃)—CH₂—OH, or —CH₂—CH(—OH)—CH₃.
 28. The method of claim 12,wherein R² is a branched C₁₋₁₂ alkyl, which is optionally substitutedone or more times by —OH.
 29. The method of claim 28, wherein R² is abranched C₁₋₁₂ alkyl that comprises branching at the α-position.
 30. Themethod of claim 29, wherein R² is isopropyl, sec-butyl, or tert-butyl.31. The method of claim 28, wherein R² is a branched C₁₋₁₂ alkyl thatcomprises branching at the β-position.
 32. The method of claim 31,wherein R² is isobutyl or 2-ethylhexyl.
 33. The method of claim 28,wherein R² is a branched C₁₋₁₂ alkyl that comprises branching at theψ-position.
 34. The method of claim 33, wherein R² is isobutyl, isoamyl,neopentyl, or 3,5,5-trimethylhexyl. 35-48. (canceled)